Synthesis of organic compounds and catalyst therefor



p 1958 E. w. RIBLETT ETAL 2,850,515

SYNTHESIS OF ORGANIC COMPOUNDS AND CATALYST THEREFOR Filed Jan. 12, 1955INVENTOR-S HENRY G. MGGR ATH EARL Wv RIBLETT BY 31, pazmw.

ATTOEZYE'Y'S ilnited States Patent SYNTI-ESIS OF ORGANIC COMPOUNDS ANDCATALYST THEREFOR Earl W. Rihlett, Tenafly, and Henry G. McGrath, Union,N. J., assignors to The M. W. Keliogg ompany, Jersey City, N. 3., acorporation of Delaware Application January 12, 1955, Serial No. 481,298

13 Claims. (6!. 260449.6)

This invention relates to an improved method for hydrogenating carbonoxides in the presence of a catalyst to produce hydrocarbons andoxygenated organic compounds. The carbon oxides treated compriseprimarily carbon monoxide and carbon dioxide, but may include also otherorganic compounds which contain the carbonyl group, such as ketones,aldehydes, acyl halides, organic acids and their salts and esters, acidanhydrides, amides, etc., and whose reaction with hydrogen to produceother oxygenated compounds and hydrocarbons is promoted by .catalystsand reaction conditions which are efiective to promote the reaction ofhydrogen with carbon monoxide. While the improved process is applicableto the hydrogenation of these compounds of carbon and oxygen, to produceboth hydrocarbons and oxygenated organic compounds, the invention isparticularly applicable to the large scale production of hydrocarbons bythe hydrogenation of carbon monoxide. This application is acontinuation-in-part of our prior and copending application Serial No.84,853, filed April 1, 1949 now Patent No. 2,702,814.

The object of this invention is to provide an improved supportedcatalyst for the hydrogenation of carbon oxide by contact with thecatalyst in finely-divided form.

Another object of this invention is to provide a novel catalystcomposition for use in the hydrogenation of carbon oxide.

Various other objects and advantages will become apparent to thoseskilled in the art from the accompanying description and disclosure.

The above-described reactions may be carried out in a highlyadvantageous manner by passing the reactants as a gas stream upwardly ina reaction zone through a mass of finely-divided solid catalyst. In oneembodiment of this invention the gas stream is passed through thecatalyst powder at a linear velocity which is effective to suspend thecatalyst in the gas stream in a dense fluidized pseudo-liquid phase inwhich the particles of catalyst circulate at a high rate. If thevelocity of the gas stream is maintained sutliciently low, the catalystmass assumes a condition which is described as pseudo-liquid for thereason that the mass exhibits many of the properties of a true liquid,particularly as to flowability and density. The gas velocity necessaryto produce this condition depends somewhat upon the character andcondition of the catalyst, but it is preferred ordinarily to pass thegas stream through the catalyst at a velocity which is sufiiciently lowto produce the above described condition but sufiiciently high withoutsubstantial entrainment t0 pr0- duce turbulence in the mass whereby theparticles circulate at a high rate throughout the mass of contactmaterial.

Under the conditions described above, the fluidized mass of contactmaterial is quite dense, resembling in this respect a settled mass ofthe same material. The density of the fluidized mass may be not lessthanhalf that of the settled mass. The fluidized catalyst mass is suspendedin the gas stream but there is no movement of the Patented Sept. 2, 1958catalyst mass as a whole along the path of flow of the gas stream. Thus,while the catalyst mass is suspended in the gas stream, it is notentrained therein. However, a small proportion of the particles of thefluidized mass may become entrained and carried away in the gas streamemerging from the dense pseudo-liquid catalyst mass.

To produce the fluidized catalyst mass the gas stream is passed into thebottom of the reactor through a relatively small inlet at an inletvelocity such that solids in the reactor are prevented from passingdownwardly out of the reactor through the gas inlet. The horizontaldimension of the reactor and the rate of flow of the gas stream into thereactor are controlled to produce in the reactor a gas velocityeffective to maintain the catalyst mass in the fluidized condition. ThisVelocity is defined ordinarily in terms of the velocity of the gasstream through an empty reactor which is referred to as the superficialvelocity. Ordinarily, superficial velocities of 0.1 to 10 feet persecond are employed for pseudo-liquid type operations; the actualvelocity depends on such 'factors as catalyst density, composition andsize.

It is preferred ordinarily in pseudo-liquid type opera tions to providea reactor having a volume substantially greater than the desired volumeof the fluidized catalyst mass. In such a large reactor the catalystforms the relativeiy dense fluidized mass described above whichj occupies the lower part of the reactor and which is referred to hereafter asthe dense phase. In the upper part of the reactor the density ofcatalyst in the gas is substantially less and of a different order ofmagnitude than the density of the catalyst in the dense phase. The upperphase may be referred to as a diffuse phase. In the diifu se phase thereis substantial disengagement by settling of solids which are liftedabove the dense phase by the gas stream. Depending upon the gas velocityand the particle size of the catalyst mass, such settling may effectsubstan; tially complete disengagement of solids from the gas stream.Ordinarily, however, a substantial proportion of the particlescomprising the catalyst mass has a free settling rate less than thesuperficial velocity of the gas stream, whereby a small proportion ofthe catalyst is carried from the reactor in the exit gas stream intheabsence of special means to effect separation of the suspended solidsfrom the gas stream. 7

Between the dense catalyst phase and the upper diffuse phase there is aninterface which is a relatively narrow zone in which the concentrationof solids in the gas stream changes from the high concentration of thedense phase to the low concentration of the diffuse phase.

In order to produce the desired turbulent pseudo-liquid condition in thedense phase, it is desirable that at least a substantial proportion ofthe contact material consist of particles whose free settling rate isless than the superficial velocity of the gas stream. The massof contactmaterial may consist advantageously of a mixture of particles varying insize from 40 to 400 microns (average diameter), although particles oflarger or smaller diameter may be present.

The pseudo-liquid type operation is initiated by charging the reactorwith the desired quantity of the contact material. Thereafter, thecontact mass in the reactor is fluidized by the passage of a gas streamupwardly therethrough at the proper Velocity. Alternatively, a gasstream may be passed through the empty reactor, while catalyst ischarged to the reactor at a rate in excess of the rate at which catalystis carried out of the reactor in the gas stream. In this manner, thedesired volume of fluidized dense phase may be built up. During theoperation it may be necessary to add catalyst to the reactorcontinuously or intermittently to replace deactivated catalyst, or toreplace catalyst carried from the reactor with the product gas stream.

V of the gases.

7 such contact. materials.

[such as thoriaor magnesia.

crystalline structure. The acid 'tr'eatment'may also The reaction isinitiated by heating the fluidized contact mass to a temperatureeffective to initiate the reaction. Thereafter, 1t1s necessary to coolthe fluidized contact mass to ma ntain the reaction temperature .at thedesired level.

It'is a feature of the pseudo-liquid method of operation for by indirectheat exchange means of the character indi V cated below in the exampleor by introducing a cold gas or vaporizable' liquid directly into thedense phase.

. Another mode of operation involves the use of sufiiciently high gasvelocities to entrain the contact material such that all of itcontinuously moves in the direction of flow The entrained contactmaterial passes from the reaction zone with the eflluent gasesto asolids separator,'.su'ch.as.a conventional settling'zone or cycloneseparator. Contact material is separated from the effluent gases andrecycled, after aerationland/or stripping, to the.

reaction. zone. The concentration of contact material in thegasesinthereaction zone is materially less than is characteristic ofdense phase operations. Generally, superficial gas velocities. above 5feet persecond areemployed,-preferablyg8 to 40 feet per second orhigher, depending on such factors as catalyst density, compositionand'size, and reaction conditions employed. As with dense phaseoperations, the reaction zone may be cooled indirectly by conventionalmeans, or directly by injection of a cooling medium therein.

The catalysts, or contact material ordinarily employed in thereaction-of hydrogen and carbon oxides, include hydrogenating metalsalone or in combination with each. other, which may 'or may not beemployed with activat'mg metal oxides and supporting materials. Thehydrogenating metals which are employed ordinarily includeihe metals ofgroup VIII of the periodic system. While metal liciron or an oxide ofiron may be employed satisfactorily without the use of supportingmaterials, it is preferred to employ the. catalytic metals or theiroxides of group VIII, particularly those metals having an atomic numberhigher than 26, such as cobalt and nickel, in combination with suitablesupports to be discussed-hereinafter. In addition activating metaloxides may be incorporated in sodium, potassium, barium0xides','etc.,fa1umin'a, silica,

For example, a catalyst may comprise metallic cobalt in combination withapproximately .onehalf to five times, preferably one to three times, itsweight of support and approximately 0.01 to 0.5, preferably 0.05 to 0.2;its'weight of a ditfieultly reducible metal oxide,

According to this invention, it has been discovered that catalysts incombination with supports of the character previously employed, such askieselguhr, are inferior,'when used as asuspension offinely-dividedpowder as described above.

a support a bentonite type clay. Bentonite clays'containmonttnorillonite as their characteristic essential ingredient. Thcsecla'ys, in many instances, however, contain certain impurities which areinjurious to the catalyst or to the property of the clay as a support.These clays may be improved ;for'use as a support in fluidized processesby acid treatment, such as'treattnent with sulfuric, hydro-' chloric andhydrofluoric acidsI Such acid treatments re-' move impurities andconvert the. clay to hydrogen montmorillonite, but, in general, these,treatments do not afiect It has been found that superior catalysts foruse as suspensions maybe produced by employing as: 65

the precipitate of'thehydrogenating metal.

improve the porosity and surface area of the support. Bentonite claysare commercially available in the market under the trade name Filtroland Super-Filtrol. Super-Filtrol is an acid treated bentonite clay andis particularly adaptable as a support for hydrogenation catalysts foruse'in processes as described.

The supported catalyst of this invention is prepared by precipitating ahydrogenating metal from an aqueous solution thereof and admixingSuper-Filtrol or bentonite clay as a slurry with the aqueous solutioncontaining The pro-. cedural steps of precipitating the hydrogenatingmetal have been found to be very important in preparing an activecatalyst of this type. Accordingly, an aqueous solution of a watersoluble hydrogenating metal salt is prepared; A second alkaline solutionis prepared.- The first solution of the hydrogenating metal is addedslowly, with stirring,

to the aqueous alkaline solution whereby a fine precipitate of thecorresponding water.insoluble.'hydrogenatingmetal salt is formed. Thebentonitesupport. may be added'to either of the solutions prior toprecipitation such that'the precipitate is efiected in the presence ofsuspended support. Alternatively, the'bentonite support'may be added tothe resulting'aqueous mixture after precipitation has been effected.Theslurry obtained in either case, after thorough mixing, is dried, andthe dried material is treated at an elevatedtemperature with a reducinggas, such as hydrogemto reduce the hydrogenating metal salt to themetal. The granular material may be ground before or after the reductiontreatment to produce the desired particle size distribution. Anypromoting agentswhich are employed, such as 'thoria and magnesia, may beincorporated by precipitating them from a solution of their 'watersoluble metal salts simultaneously with the precipita- These include'alkalis such as.

tion of the hydrogenating metal salt, or after the precipitation of thehydrogenating metal salt.. It is important, in' preparing the catalyst,to add the solution containing the.

water soluble hydrogenating metal salt to the alkaline so- 'lution inorder to precipitate the water insoluble hydrogenating metal salt;Employing the reverseope ra'tion of adding the alkaline solution tothesolution of the water soluble hydrogenating-metal salt does not produceas" active a catalyst as the method employed in the present process;Thisdiiference inactivity may be" due .tothe. colloidal nature of theprecipitate, but such theory should. not be construed as unnecessarylimiting to the present invention. In any .event, the catalysts preparedas set forth herein are more active and produce'higher yields ofnormally liquid organic compounds than catalysts prepared by. othermethods. In the case of cobalt, the dried.

precipitate, prior to reduction, is gray-brown in color, and afterreduction is black.

The hydrogenating catalysts containing; supports pre- 'viously employedarenot suitable for use in the hydrogenating of a carbon oxide becausetheir activities are relatively "low- Moreover, these previously used.supportedcatalysts are.,diffic.ult to maintain in-a fluidizedcondition'when employed 'in' fluidized operations, because of therelatively narrow range of velocities by which they can be fluidized. Onthe other hand, the bentonitel type support, when present in appropriateproportions;

results ina hydrogenation catalyst of optimum activity.

rbr the hydrogenation .of carbon oxides to normally liquid V .Theinvention'will. be described'in more organic compounds, andthe resultingcatalyst can be maintained. in a.fluidized condition over relativelywide gas velocities and reaction conditions;

erence to the specific examples of. theuse. .of the imployed. incarrying out the in the example; i Referring to the drawing, reac tor 1detailby. refconsists of a length;

of extra heavy 2-inch steel pipe which is 153 inches long and has insideand outside diameters of 1.94 inches and 2.38 inches, respectively.Reactor 1 is connected by a conical section 2 to an inlet pipe 3 made ofextra heavy half-inch steel pipe having an inside diameter of 0.55 inch.Reactor 1 is connected at the top, by means of conical section 4, withan enlarged conduit 5 comprising a length of 6-inch extra heavy steelpipe having an inside diameter of 5.76 inches. Conical section 4 andconduit 5 constitute an enlarged extension of reactor 2 whichfacilitates disengagement of catalyst from the gas stream after passageof the latter through the dense catalyst phase.

Conduit 5 is connected by means of manifold 6 with conduits 7 and 8which comprise other sections of extra heavy 6-inch steel pipe. Conduits7 and 8 contain filters 9 and 10 which are constructed of porousmaterial which is permeable to the gas and vapors emerging from thereaction zone but substantially impermeable to the catalyst particlescarried by entrainment in the gas stream. Filters 9 and 10 arecylindrical in shape and closed at the bottom ends. They are dimensionedin relation to conduits 7 and 8 to provide a substantial annular spacebetween the filter and the inner wall of the enclosing conduit for thepassage of gases and vapors and entrained catalyst upwardly about theouter surface of the filter. The upper ends of filters 9 and 10 aremounted in closure means 11 and 12 in a manner whereby the gases andvapors must pass through either filter 9 or filter 10 to reach exitpipes 13 and 14. Each of filters 9 and 10 is approximately 36 incheslong and 4 /2 inches in outside diameter, the filter walls beingapproximately /4 of an inch thick.

The greater part of reactor 1 is enclosed in a jacket 15 which extendsfrom a point near the top of the reactor to a point sufficiently low toenclose the 3 inch length of conical section 2 and approximately 5inches of pipe 3. Jacket 15 comprises a length of extra heavy 4-inchsteel pipe having an inside diameter of 3.83 inches. The ends of jacket15 are formed by closing the ends of the 4-inch pipe in any suitablemanner, as shown. Access to the interior of jacket 15 is provided by anopening 16 in the top thereof through a 2-inch steel pipe. Jacket 15 isadapted to contain a body of liquid for temperature control purposes,such as water, or Dowtherm (a constant boiling mixture of diphenyl anddiphenyl oxide). The vapors which are evolved by the heat of reactionare withdrawn at 16, condensed, and returned through 16 to the body oftemperature control fluid in jacket 15. The temperature control fluid injacket 15 is maintained under a pressure at which the liquid boils atthe temperature desired in jacket 15. Heating means, not shown, areprovided in connection with jacket 15 to heat the temperature controlfluid therein to any desired temperature.

In order to show all the essential parts of the reactor and associatecatalyst separation means on a single sheet, a large proportion of theapparatus has been eliminated by the breaks at 17 and 18. For a clearunderstanding of the relative proportions of the apparatus reference maybe had to the over-all length of the apparatus, from the bottom ofjacket 15 to exit pipes 13 and 14, which is 224 inches. In each ofbreaks 17 and 18 the portion of the apparatus eliminated is identicalwith that portion shown immediately above and below each break.

In the operations carried out in the apparatus of the drawing thecatalyst recovery means comprising filters 9 and 10 is effective toseparate substantially completely entrained catalyst from the outgoingstream of gases and vapors. The disengagement of solids from the gasstream is promoted by the lowered velocity of the gas stream in conduit5 and remaining solids are separated on the outer surfaces of filters 9and 10. The latter are employed alternatively during the operation sothat the stream of gases and vapors and entrained solids passes fromconduit 5 through either the left or right branches of manifold 6 intoconduit 7 or conduit 8. During the alternate periods, the filter whichis not in use is subjected to a back pressure of inert gas which isintroduced at a rate sufiicient to dislodge catalyst which hasaccumulated on the outer surface of the filter during the active period.Such blow-back gas and dislodged catalyst flows downwardly in theconduit enclosing the filter and into manifold 6 in which the blow-bacgas is combined with the reaction mixture flowing upwardly from conduit5. The greater part of the catalyst thus dislodged settles downwardlyinto the reactor and is thus returned for further use.

In the operation of the apparatus of the drawing the desired quantity ofpowdered catalyst is introduced directly into the reactor through asuitable connection, not shown, in conduit 5. After any desiredpreliminary activation treatment the temperature of the fluid in jacket15 is adjusted, by the heating means mentioned above and by the pressurecontrol means, to the temperature desired to be maintained in jacket 15during the reaction. After the catalyst mass has reached the reactiontemperature, the introduction of the reaction mixture through pipe 3 isinitiated. The reaction mixture may be preheated approximately to thereaction temperature prior to its introduction through pipe 3, or thereactants may be heated to the reaction temperature by the passagethereof through that portion of pipe 3 which is enclosed by jacket 15and by contact with the hot catalyst. It will be understood,furthermore, that the enclosure of pipe 3 in jacket 15 is not necessaryto the invention and that the reactants may be heated to the reactiontemperature solely by contact with the hot catalyst.

Pipe 3 is dimensioned with respect to reactor 1 and the desiredsuperficial velocity whereby the velocity of the gases passing throughpipe 3 is sufiiciently high to prevent the passage of solids downwardlyinto pipe 3 against the incoming gas stream. A ball check valve, notshown, is provided in pipe 2 to prevent solids from passing downwardlyout of the reactor when the gas stream is not being introduced into pipe3.

EXAMPLE I A catalyst for promoting the reaction of carbon monoxide withhydrogen was prepared as follows: 10,000 grams of cobalt nitrate, Co(NO.5H O, and 1910 grams of magnesium nitrate, Mg(NO .6H O, were dissolvedin 50 liters of treated water. 6100 grams of sodium carbonate, Na CO HO, were dissolved in 50 liters of treated water. Both solutions wereheated to the boiling point and the nitrate solution was then added tothe carbonate solution with continuous stirring. After the resultingmixture had been stirred thoroughly, 4,000 grams of finely-dividedSuper-Filtrol (previously dried at 900 F for 1.5 hours) at a temperatureof 210 F. were added to the solution with vigorous stirring. Afterthorough stirring, the resulting mixture was then filtered under apressure of 30 pounds per square inch gage. The filter cake was washedin the filter with gallons of treated water at F. The washed filter cakewas dried overnight at room temperature by means of a blower. Thepartially dried material was dried at 210 F. to a moisture content ofabout 54% and was then extruded through inch dies. The extruded materialwas then dried overnight at 210 F. to obtain a product having a moisturecontent of about 16%. This material was then ground to '7 produce agranular-mass finer than 6 mesh butfcoarser than ZO mesh. The granularmaterial thus produced was reducedin an oven by means of a circulatingstream of' hydrogen from which water and CO were removed con-'tinuously. The temperatureof the mass of catalyst during this operationwas raised to a final temperature of 700 F. during which; time theproduction'of water ceased. The

. reduced catalyst was then ground in an atmosphere of to a powderof thedesired size.

The following is a screen analysis of this powders This catalyst had'the following approximate composition in parts-by weight: Co:0.15MgO:2.0 -Super-Filtrol.

1 should be understood as a numerical part of the first component of thecatalyst. V

Reactor 1 was purged by means of CO and, while a small stream-of CO waspassed through reactor 1, 9

poundsof the catalyst prepared as described above were 7 introducedfwhile' maintained in an atmosphere of C0 1 'The' catalyst mass was thenheated to approximately 300 F. by heating the water bath in jacket 15.At that point a small stream of hydrogen was substituted for the COasjthe aerating medium. Heating was continued to a temperature ofapproximately 360.F. at which point the passage of astream of reactiongas, consisting essentially of H and CO in the ratio of approxirnately.2:1, V

wasinitiated. The reaction temperature was then-raised during'a periodof Il hours to 400i F. V This operation was continued for approximately650 4 hours during which time "the gas waspassed through the reactor atvarying'experimental conditions. The reaction 7 a temperature variedfrom 380 F; to 425 F. The pressure varied from atmospheric to 50 poundsper square inch (gage). The feed gas, which consisted substantiallyentirely of H 'and CO in ratios of 2:1 to 3:1, was charged to thereactor at space velocities of 330 to 875 volumes of 'gas (measured atstanda'rd conditions of temperature and pressure) per volume of densecatalyst phase per hour. A high rate of conversion to liquid hydrocarbonproductswas maintained throughout the operation, which wasterminatedarbitrarily. Throughout this operation 7 the catalytic contactmass exhibited the desired dense fluidized pseudo-liquid condition withthe result that uniform temperature conditions were maintainedthroughout the reactor at all times. 'At no time during the operationwas there observed any accumulation ofdeposits on the contact materialwhich interferred with .the fluidized condition. Examination of thecatalyst after the termination of the operation showed it to be afinelyaiivided nonadherent easily fluidizable material. After 516 hoursof i the operation the catalyst was revivified'by treatment with astream of hydrogen at 700850 F. for. 6 hours;

' The function of'this regeneration treatment appeared to be thered'uction of oxides formed on the catalystsurface during the operationratherjthan the removal of waxy deposits.

';For a specific example of the; operating conditions for productionrate in this oper'atiomrefere'nce is made to a 12 hour period occurringafter .147 hours of operation.

In th is period the feed gas consisted of 65.5% .H 29.7% C0 and 4.8%inerts; This gas was charged through pipe 3 ate temperattireof2,l,7;F;,-,at.the' rate of. 118.5 standard cubic feetper'hour under apressure equivalent toan outlet pressure of 44 pounds per square inch.This produced a superficial inlet velocity of 0.62 feet per second. Theresulting dense fluidized mass of contact material rose to'a height of8.6 feet in 15 seconds, the reactor'con" responding to a densityof 46pounds per cubic foot.

The space velocity 'was, therefore, 685 standard cubic V feet per hourper cubic foot of fluidized. contact mass. This corresponded to 2.54standard liters of gas per hour per gram of cobalt. During this period,theaverage temperature in the reactor varied from a maximum of.

413 F. at a point 2.5 feet above pipe 3 to a minimum 386 F. at a point 6inches above pipe 3. The average temperature'in the dense phase duringthis period was 4 402 F; This resulted in the reaction of 63.4% of theCO charged to the operation. Of this, 5.1% was converted to hydrocarbonshaving molecular weights lower than that of propylene and 57.9% wasconverted to a liquid hydrocarbon product comprising hydrocarbons of 3or more carbon atoms per molecule; The yield of this latter product wasequivalent to l49 cc./m. of synthesis gas. The fraction ofthis oil whichcondensed substantially at roomtemper-ature contained 6.9 mol percentolefins.

EXAMPLE II A catalyst was prepared in accordance with the followingprocedure:

A cobalt nitrate solution was prepared by dissolvlng 1 0,000 grams ofCo(NO .6H O in 50 liters of water.

A sodium'carbonatesolution was prepared by dissolving 6,100 grams of NaCO .H O in 50 liters of water. With both solutions at the boiling pointthe cobalt nitrate solution was added with stirring to the sodiumcarbonate solution. After thorough stirring, 4,000 grams of driedSuper-Filtrol preheated to 180200 F. were added with vigorous stirring.V The slurry thus obtained was filtered andfthe filter cake wasreslurried in gallons of treated water." After standing for severalhours, the slurry' thus obtained was heated to boiling'with vigorousstirring, after which the slurry was filtered again. During thisoperation the filter'cake was washed with 300 gallons of hot treatedwater. The filter cake thus obtained had a water content ofapproximately 70 weight percent. This material was partiallydried atroom temperature to. a water content of approximately. 57% and was the'nextruded through a 9% inch diameterorifice. Thfe extru d ed material washeated overnight in an oven at. 420 'F. The material thus obtained wasin the form of hard lumps and had a water content of approximately 7.6weight percent. This material was then ground in a Braun disc mill andscreened to collect material passing through 'a mesh sieve. 'Ma'terialwhich did not pass the sieve was recycled to reduce the batch to a sizesmaller than 40 mesh.

The following is1a screen analysis of this, powder:

Size range:

. 60/80 6.0 0 .80/ 4.0, 100/120 1.0' 1120/ 9.4 140/200 12.9 ZOO/pan 60.8

. 6.3 pounds of this material were charged to reactorrl, this amountbeing chosen toproduce 5.8 pounds of cat alyst in the reactor'afterreduction. The unit was flushed out with nitrogen and then hydrogen waspassed in through :pipe 3. Jacket '15 was filled with a suitabletemperature control fluid such 'as Dowtherm, and by heating this fluidin the manner described above the tempperature of V the cataly'st masswas gradually raised; After the tent g Weight percent 40+ 5.0

perature of the catalyst was raised to 400 F. the rate of introductionof hydrogen was in increased to 40 cubic feet per hour and thetemperature was raised, While operating at that velocity, to 700 F. Thisoperation was continued until the formation of water ceased, after whichthe hydrogen flow rate was lowered to cubic feet per hour and thetemperature was lowered to 300 F. The catalyst composition was Co:2Super-Filtrol.

The Dowtherm was then removed from jacket 15 and replaced with water ata temperature equivalent to a catalyst temperature of 300 F. Theintroduction of feed gas, consisting essentially of two parts ofhydrogen and one part of carbon monoxide, was then initiated at a spacevelocity of 333 standard volumes per hour per volume of dense catalystphase. The temperature was raised rapidly during two hours to 360 F. andthereafter was raised to 400 F. in a space of 14 hours. The operationwas continued thereafter under various experimental conditions for 1,115hours at the end of which time the unit was shut down arbitrarily andthe catalyst withdrawn for examination. During this time the averagetemperature in the reaction zone varied from a minimum of 380 F. to amaximum of 469 F. and the pressure varied from atmospheric to 50 poundsper square inch (gage). The feed gas consisted substantially of hydrogenand CO in ratios of 2:1 to 3:1 throughout this period, and it wascharged to the reactor at space velocities varying from 175 to 1200standard volumes per hour per volume of dense catalyst phase.

Throughout this period the contact material was observed to remain inthe desired dense fluidized pseudoliquid condition whereby uniformtemperature conditions throughout the dense phase were observed. Therewas no deposition of material on the surfaces of the contact materialwhich interfered in any way with the fiuidizable material of thatcharacter. At the end of this operation, as was the case at the end ofExample I, the accumulation of deposits on the contact material wasfound to amount to less than 1 weight percent of the contact material.Such deposits consisted of waxy oil and carbon. In spite of suchdeposits, however, the contact material remained perfectly dry andnon-adherent throughout the operation.

For a specific example of the conditions and product obtained duringthis operation reference is made to a 24 hour period occurring after 531hours of operation. During this operation the average temperature in thereactor varied from appoximately 450 F. at a point 6 inches above pipe 3to 433 F. at a point 6.5 feet above pipe 3. During this operation thefeed gas, containing 30.0% C0, 61.7% H and small amounts of CO CH and Nwas introduced through pipe 3 at a pressure of 47 pounds per square(gage). This produced a pressure of 45 pounds at the outlet. Under theseconditions the dense bed had a depth of approximately 5.5 feet,corresponding to a density therein of 49 pounds per cubic foot. Theinlet superficial velocity was 0.75 feet per second. The feed gas wascharged at the rate of 1170 cubic feet (measured at standard conditionsof temperature and pressure) per hour per cubic foot of dense phase.This corresponded to 5.0 liters of gas per hour per gram of cobalt. Thegas was charged at room temperature and was preheated to the reactiontemperature during the passage thereof through pipe 3 and by contactwith the contact mass. 40% of the carbon monoxide charged during thisperiod was reacted, of which 11.4% was converted to hydrocarbons oflower molecular weight than propylene and 27.0% was converted to aliquid product composed of hydrocarbons of three or more carbon atomsper molecule. The material that condensed from the reactants at roomtemperature and operating pressure had an initial boiling point of 194F. and an end point of 657 F. The olefin content of this hydrocarbonliquid was 2.3%.

' Hours on condition 10 EXAMPLE IH This example shows a comparisonbetween a catalyst prepared in the manner of this inventionsubstantially the same as that prepared in Example I, and a catalyst ofthe same composition but prepared by adding the alkaline solution to thesolution of the water soluble salt of the hydrogenating metal. Thecomposition of the catalyst prepared by both of these methods was0010.15 MgO:2.0 Super-Filtrol (acid treated bentonite). All the solutionconcentrations, temperature of precipitation, etc., were identical withboth preparations. During the precipitation of the catalyst prepared inthe manner of this invention, no difliculty was encountered. On theother hand, during the precipitation of the catalyst prepared byaddition of the alkaline solution to the aqueous solution of the watersoluble salt of the hydrogenating met-a1, rapid evolution of carbondioxide was noticed, which caused frothing of the mixture. The evolutionof carbon dioxide required that the precipitation step be elfectedslowly.

The catalysts thus prepared were tested in petroleum atmospheric testunits. Each catalyst was charged to the respective unit in the form of 8to 12 mesh fragments. The catalysts were reduced at 800 F. for fourhours with hydrogen. Thereafter, a synthesis feed gas comprisinghydrogen and carbon monoxide in the ratio of about 1.7:1 was passedthrough the reduced catalysts in the respective unit at a temperature of350 F. The catalyst prepared by method I was that prepared by the methodof this invention. The catalyst prepared by method II was that catalystprepared by adding the alkaline solution to the aqueous solution of thewater soluble salt of the hydrogenating metal. The temperatures of thetest units were raised to about 370 F. for test purposes. The resultsobserved during the test periods after reaching 370 F. are summarized inthe following table:

Comparative tests of supported cobalt catalyst Prepared by method I IIThe results observed during the test indicate substantially the sameactivity of the catalyst during the initial period of operation but,upon use, the catalyst prepared by method 11 became less active withlower yields and lower conversions. Gn the other hand, upon use, thecatalyst prepared by method I indicated substantially improved yieldsand increased covnersion. The catalyst prepared by method I wasdefinitely superior to the catalyst prepared by method II.

The results obtained with various bentonite type supported catalysts areshown in the following table employing comparable conditions ofoperation. All of these catalysts shown in the following table wereprepared in the manner described in this application. Although the metalsalt was precipitated, in most instances, by a sodium carbon-atesolution, an ammonium carbonate or potassium carbonate solutions couldhave been used and actually have been used in the preparation of othersimilar catalysts.

' ganic compounds.

op u

Composition Cat. No. 7 V j V Temp Oil, H 0,

615. ccJmfi cc./n1.

Coz2SF -Q 215-2B 408 115 178 O:0.471\/I110:2SF V 241 457 87 1 135 Co 015Wg0 2SF- '248 383 174 231 00:0.15Mg0z4S 249 399 92 173 (30.015l\/IgO.6SF 250 364 2 7 Co:0.15Mg0:8SF 251 389 ,0 4 Fe:1.25SF 263-2 1460 '23 25 Fe.0.3Cu 0 05N1 1 25SF 265-2 460 74 37 C0:0.25ThO2:2S 270 405171 205 C0:O.25ThOz:1SF 271 390 168 203 C0 0 5Z110:2SF 272-3 394 110 158C0 0 5Z110.1SF 273 375 120 188 Fe:0.3Cu:0.05Co 280 460 48 57Fe:0.3Cu:1.25SF 281 460 '24 32 Fe:0.3Cu:0.05Ni:2SF 282 475 24 34 Fe0.3Cu 0.0500 0.03Al203 1.25SF (0.5% K20) 295 450 36 51 Fe 0.3011 0.1001.25SF (0.5%

299 460 45 67 300 454 46 47 Fe:0.3Cu: 5C0:1.25SF 301 450 53 146 VFe:0.5AlzO :1.25SF (0.1% K 0). 302 455 23 30 Fe:0.05CIzO :1.25SF (0.1%K20)" 304 475 39 Fe 0.3Gu 0.0500: 1.25SF (1.0%

NazB4O7); 305 460 42 53 315 390 126 199 K)"; 327 V 465 64 .46Fe:0.3Cu:0.02MnO:1.25SF p 329 465 60 49 Fe:0.3Cu:0.02MgO:1.25SF 330 47046 31 Fo:0.3Cu:0.02MnO:1.25SF (2.0%

K) 335 475 88 33 Fe:0.02MnO:1.25SF (0.5% K20) 336 460 50 48Fe:0.3Cu:0.1TiO2:1.25SF (0.5%

K10) 337 460 84 47 Fe 0.30m 0.02Mn0 00314120 i The tests shown in theabove table indicate several conclusions with regard to thefSuper-Filtrol supported catalysts. It is preferred to maintain theratio of Super- Filtrol to cobalt less'than 5. since higher quantitiesof fSuper-Filtrol result in a substantially inactive catalyst. A4-component catalyst, including cobalt," magnesia} alumina andSuper-Filtrol, was found to be highly active and, in some cases, moreactive than the 3-component catalyst without the alumina. In this4-component catalyst the alumina content should be maintainedtbelowabout. 01 part by weight with respect to cobalt, thepreferred rangebeing between about 0.01 and ab0ut10.05.alumina. Another 4-cornponentcatalyst comprising iron, copper, cobalt and Super-Filtrol was also.found to be highly, active and superior to the 3-component catalystWithout the use of cobalt. Another 4-cornponent catalyst similar to theabove, containing nickel instead of cobalt was 7 also found to be a goodsynthesis catalyst. As a general rule for all catalysts cobalt was superior' to'nickel either when the cobalt was the base material or whenthe cobalt was employed in" small quantity as'a promoter. With the4-component iron catalyst a small amount of' alkali, such as potassiumoxide, increased the activity of the catalyst for the production ofnormallyliquid or-- The optimum amount of potassium oxidewas'approximately 0.5% byweight calculated as: the oxide. Various otherconclusions may be obtained by examination of the above table.

' r In generalithe'temprature of reaction employing bentonite supportedcatalystsis between about 350 and about 550: F., and preferably thetemperature is maintained above about 435 for satisfactory operation ina fluidized system. In all instances the temperature of reaction ismaintained below the temperature at, which substantial degradationreactions occur. I At temperatures 7 gage are generally. employed,preferred pressures being between about atmospheric and about 50 poundsper square inch-gage. Higher space velocities are associated with highertemperatures and higher pressures. The hydrogen to carbon monoxideratio'in the total feed gas entering the reactor is maintained betweenabout 1:1 to about 5 :1 or higher, and generally the mol percent ofcarbon monoxide is less than percent in the total gas entering thereactor. .Tlie hydrogen andcarbon monoxide are the principal reactantsof the feed, although this does not excludethe use of-othergases, suchas nitrogen,

methane, etc., as diluent gases, or the use of olefins and products ofthe process which may enter into reaction with the products of thehydrogenation reaction or with'the re- 'actants themselves. In any case,however, the primary. reaction and the conditions employed are such thatcanbon monoxide is hydrogenated to produce normally liquid organiccompounds as the principal product of the process. For a more completediscussion of the operating conditions and synthesis technique ingeneraL'reference may. be had to application.S, N.-47,184, filedSeptember l,- 1948,-now.U. S. Patent No. 2,615,035, by Louis C. Rubin,'f

Earl w. Riblett and Henry G. McGrath.

pWeclaim: i

1. A process torltheihydrogenation of a carbon oxidef.

to produce normally liquid organic compounds which comprlsesfiowingagaseous mixture comprising hydrogen and a carbon oxide as theprincipal reactantsupwardly,

in areaction zone in'contact withia finely divided contact materialcomprisingin parts by weight lpart iron, be tween about 70.1 and about 1part of copper, between,

about 0.5 and about 5 parts by weight of a bentonite clay and betweenabout 0.01 and about 0.5 part of cobalt,

passing said gaseous mixture, through said reaction'zone" at a velocityeflective-to suspend said finely divided con tact materialin' gasestherein, maintaining a temperature of reaction between about 3506 F. andabout 500 F., and

withdrawing'irom said're'actionzone a gaseouseflluerit: contammgnormallyliquid organic compounds.

' :2.A process for the hydrogenation of carbon monoxide to: producenormally liquid organic compounds therefrom; which comprisescontinuouslyiflowing a' gaseous mixture comprisinghydrogen and carbonmonoxideas the principal reactants; upwardly ina reaction zone through amass of finely-divided contact material comprising in parts by weight 1part iron, between about 0.1- and about 1 part of copper, between about0.5 and about" 5 parts of a bentonite clay andbetween about 0.01. and

- ab0ut .0.5 part of cobalt, passing said gaseous mixture through saidmass at a velocity effective to. suspend said standard volumesofreactants per hour per volume'fluidized dense phase, and withdrawingfrom said reaction V zone a gaseous efHuent-containing normally liquidorganic compounds as products of the process.

3. The process of claim 2 in which the mass of finely divided contactmaterial comprises. iron in combination witha metal oxide promoter-14.;The process ofclaim 3 in which fsaid oxide;

promoter is manganese oxide. 7

5. The process of claim 3 in which said metal oxide promoter ismagnesia.

6. The process of claim 3 in which said metal oxide promoter is alumina.

7. The process of claim 3 in which said metal oxide promoter is chromiumoxide.

8. The process of claim 3 in which said metal oxide promoter is titania.

9. A process for the hydrogenation of carbon monoxide to producenormally liquid organic compounds which comprises continuously flowing agaseous mixture comprising hydrogen and carbon monoxide as the principalreactants upwardly in a reaction zone through a mass of finely-dividedcontact material comprising in parts by weight one part iron, betweenabout 0.1 and about 1 part of copper, between about 0.5 and about 5parts of a support consisting essentially of an acid treated bentoniteclay, between about 0.01 and about 0.5 part of cobalt and a minor amountof an alkali, passing said gaseous mixture through said mass at avelocity effective to suspend said mass in said gas stream in a densefluidized pseudo-liquid condition in which the particles of said contactmaterial circulate in said mass at a high rate, maintaining atemperature of reaction between about 350 F. and about 500 F. and aspace velocity between about 50 and about 5000 standard volumes ofreactants per hour per volume of fluidized dense phase, and withdrawingfrom said reaction zone a gaseous etfluent containing normally liquidorganic compounds as products of the process.

10. A contact material comprising in parts by weight 1 part iron,between about 0.1 and about 1 part of copper, between about 0.5 andabout 5 parts by weight of a bentonite clay and between about 0.01 andabout 0.5 part of a reducible metal oxide of the group consisting ofthon'a and magnesia.

11. A four-component catalyst comprising in parts by weight 1 part iron,between about 0.1 and about 1 part 14 of copper, between about 0.5 andabout 5 parts by weight of a bentonite clay and between about 0.01 andabout 0.5 part of cobalt.

12. The catalyst of claim 11 in which an alkali metal oxide is presentas a promoter.

13. A process for the hydrogenation of carbon monoxide to producenormally liquid organic compounds therefrom which comprises continuouslyflowing a gaseous mixture comprising hydrogen and carbon monoxide as theprincipal reactants upwardly in a reaction zone through a mass offinely-divided contact material comprising in parts by weight 1 partiron, between about 0.1 and about 1 part of copper, between about 0.5and 5 parts of a bentonite clay and between about 0.01 and about 0.5part of cobalt, passing said gaseous mixture through said mass at avelocity eflective to suspend said mass in said gas stream in a densefluidized pseudo-liquid condition in which the particles of contactmaterial circulate in said mass at a high rate, maintaining atemperature of reaction between about 350 F. and about 500 F. and aspace velocity between about 300 and about 2000 standard volumes ofreactants per hour per volume fluidized dense phase, and withdrawingfrom said reaction zone a gaseous eflluent containing normally liquidorganic compounds as products of the process.

References Cited in the file of this patent UNITED STATES PATENTS1,801,382 Wietzel et a1 Apr. 21, 1931 2,348,418 Roesch et al. May 9,1944 2,365,029 Voorhies Dec. 12, 1944 2,414,276 Sensel et al. Jan. 14,1947 2,417,164 Huber Mar. 11, 1947 2,437,051 Sensel et al. Mar. 2, 19482,443,673 Atwell June 22, 1948 2,702,814 Riblett et a1. Feb. 22, 1955UNITED STATES PATENT UFFTGIE CERTIFICATE OF connscmom Patent No. 2, 850,515 September 2, 1958 Earl W. Rihlett et a1,

It is hereby certified that error appearsh in the printed specificationof the above numbered patent requiring correction and, that the saidLetters Patent should read as corrected below.

Column '7, line 59, for "interferred" read w interfered column 8, line59, in the table under the heading, "Weight percent", for "5 ,0" read awTrace 7 line 61, under the heading, "Weight percent", for "60" read m6,9 same table, line 64, under the heading, "Size range", for "1120/140read 120/140 same column 8, line '74, for "tempperature" readtemperature column 9, line 23, for "469 F, read 460 F. line 52, for "COread u 00 line 54, after "square" insert inch column 10, Example III, inthe table, first column thereof, under the heading, "Results", for"Ggntraction" read Contraction same column 10, line 62, for "covnersion"read m conversion column 12, line 9, for "300 to 20" read 300 to 2000column 14, list of references cited, the third reference, for "Voorhies"read es Voorhis, Jr. the fifth reference, for "Huber" read Huber, Jr,

Signed and sealed this 10th day of March 1959,

(SEAL) Attest:

KARL H, AXLINE ROBERT Ca WATSON Attesting Officer Commissioner ofPatents

1. A PROCESS FOR THE HYDROGENATION OF A CARBON OXIDE TO PRODUCE NORMALLYLIQUID ORGANIC COMPOUNDS WHICH COMPRISES FLOWING A GASEOUS MIXTURECOMPRISING HYDROGEN AND A CARBON OXIDE AS THE PRINCIPAL REACTANTSUPWARDLY IN A REACTION ZONE IN CONTACT WITH A FINELY DIVIDED CONTACTMATERIAL COMPRISING IN PARTS BY WEIGHT 1 PART IRON, BETWEEN ABOUT 0.1AND ABOUT 1 PART OF COPPER, BETWEEN ABOUT 0.5 AND ABOUT 5 PARTS BYWEIGHT OF A BENTONITE CLAY AND BETWEEN ABOUT 0.01 AND ABOUT 0.5 PART OFCOBALT, PASSING SAID GASEOUS MIXTURE THROUGH SAID REACTION ZONE AT AVELOCITY EFFECTIVE TO SUSPEND SAID FINELY-DIVIDED CONTACT MATERIAL INGASES THEREIN, MAINTAINING A TEMPERATURE OF REACTION BETWEEN ABOUT350*F. AND ABOUT 500*F., AND WITHDRAWING FROM SAID REACTION ZONE AGASEOUS EFFLUENT CONTAINING NORMALLY LIQUID ORGANIC COMPOUNDS.